Luminescent crystals and manufacturing thereof

ABSTRACT

The present invention relates to the field of luminescent crystals (LCs), and more specifically to Quantum Dots (QDs) of formula M 1   a M 2   b X c , wherein the substituents are as defined in the specification. The invention provides methods of manufacturing such luminescent crystals, particularly by dispersing suitable starting materials in the presence of a liquid and by the aid of milling balls; to compositions comprising luminescent crystals and to electronic devices, decorative coatings; and to intermediates comprising luminescent crystals.

This application is a continuation of U.S. application Ser. No.17/149,176 filed Jan. 14, 2021, which is a continuation of 15/745,839filed Jan. 18, 2018, now U.S. Pat. No. 10,920,137 issued Feb. 16, 2021,which is a national phase of International Application No.PCT/CH2016/000081 filed May 25, 2016 and claims priority to EuropeanApplication No. 15002279.6 filed on Jul. 31, 2015, all which areincorporated herein by reference.

The present invention relates to the field of luminescent crystals(LCs), and more specifically to Quantum Dots (QDs). The inventionprovides methods of manufacturing such luminescent crystals, tocompositions comprising luminescent crystals and to electronic devices,decorative coatings and intermediates comprising LCs.

Luminescent Crystals, specifically Quantum Dots, are a known class ofmaterials. Such QDs find many applications in industrial and commercialproducts, including electronic devices, such as light emitting diodes ordisplays.

Loredana Prodesescu et al. (Nano Lett., 2015, 15, 3692-3696) discloses anew class of luminescent quantum dots (QDs) of high quality. QDs weresynthesized with cheap chemicals and with very high size precision; QDsize was controlled by adjusting the synthesis parameters such astemperature and reaction time. However, only very small amounts weresynthesized, as the method is difficult to control (due to the very fastparticle growth kinetics of this material composition) and difficult inscale-up. Further, the reaction is non-stoichiometric, resulting in alarge amount of by-products. Furthermore, the reaction can only beconducted in high-boiling solvents like octadecene (due to the highreaction temperatures) which requires a solvent-exchange if the QD's areneeded in a low-boiling solvent like toluene for the final application.This synthesis route is known as “hot injection method”, using standardlaboratory equipment. Due to these disadvantages, the method ofsynthesizing QDs is commercially not attractive rendering the QDsexpensive.

Pfenninger et al (WO2007109734) discloses similar materials but obtainedin the form of thin films by vacuum deposition. Again, suchmanufacturing methods are considered disadvantageous.

Guo et al (WO2014/007966) discloses standard luminescent QDs of thecore-shell type based on CdSe or InP further comprising C5-C8 carboxylicacids. The standard CdSe and InP require a semiconducting shell ofbigger bandgap (e.g. ZnS) in order to reach desired opticalfunctionality. This additional synthetic step increases further theirprice, what is disadvantageous for a number of applications.

Dandang Zhang et al (JACS 2015, p. 9230-33) disclose solution phasesynthesis of cesium lead halide perovskite nanowires. Like Prodesescu,cited above, the document discloses the hot injection method usingstandard laboratory equipment to obtain nanowires. Such nanowires are noquantum dots.

Kojima Akihiro et al (JP2014078392) disclose electro-luminescentelements comprising perovskite compounds. The perovskites are obtainedby a specific solution process, termed melt-dissolving. This is abottom-up approach comprising the step of crystallizing the targetcompound. Such processes are difficult in upscaling and difficult tocontrol.

Thus, it is an object of the present invention to mitigate at least someof these drawbacks of the state of the art. In particular, it is an aimof the present invention to provide improved manufacturing methods ofLCs/QDs. It is a further aim to provide new materials comprising LCs/QDssuitable for a wide variety of applications, including electronicdevices, and optical devices and decorative coatings.

These objectives are achieved by a method for manufacturing luminescentcrystals as disclosed herein, an ink containing the luminescent crystalsand a surfactant, an intermediate good including a sheet-like substratecoated with at least one layer comprising a composition containing theluminescent crystals as disclosed herein and the uses of the compositionas disclosed herein. Further aspects of the invention are disclosed inthe specification and independent claims, preferred embodiments aredisclosed in the specification and the dependent claims. The inventionparticularly provides for

-   -   a method for manufacturing luminescent crystals, specifically        quantum dots (1^(st) aspect);    -   compositions in the form of a suspension, also termed “ink”, or        “pre-polymer dispersion”, and its uses (2^(nd) aspect);    -   a solid polymer composition and its uses (3^(rd) aspect);    -   an intermediate good (4th aspect);    -   a device, including electronic devices, optical devices and        articles comprising a coated surface (5^(th) aspect);    -   a method for manufacturing of a polymer composition (6th        aspect);    -   a method for manufacturing an intermediate good (7th aspect);        and    -   a method for manufacturing a device (8th aspect).

The present invention will be described in detail below. It isunderstood that the various embodiments, preferences and ranges asprovided/disclosed in this specification may be combined at will.Further, depending of the specific embodiment, selected definitions,embodiments or ranges may not apply.

Unless otherwise stated, the following definitions shall apply in thisspecification:

The terms “a”, “an,” “the” and similar terms used in the context of thepresent invention are to be construed to cover both the singular andplural unless otherwise indicated herein or clearly contradicted by thecontext. Further, the terms “including”, “containing” and “comprising”are used herein in their open, non-limiting sense. The term “containing”shall include both, “comprising” and “consisting of”.

Percentages are given as weight-%, unless otherwise indicated herein orclearly contradicted by the context.

The term “luminescent crystals” (LC) is known in the field and relatesto nanocrystals of 2-50 nm, made of semiconductor materials. The termcomprises quantum dots, typically in the range of 3-15 nm andnanocrystals of up to 50 nm. Preferably, luminescent crystals areapproximately isometric (such as spherical or cubic). Particles areconsidered approximately isometric, in case the aspect ratio(longest:shortest direction) of all 3 orthogonal dimensions is 1-2.

LCs show, as the term indicates, luminescence. In the context of thepresent invention a luminescent crystal typically is asingle-crystalline particle spatially separated from other particles dueto the presence of a surfactant. It is a semiconducting material whichexhibits a direct bandgap (typically in the range 1.1-3.8 eV, moretypically 1.4-3.5 eV, even more typically 1.7-3.2 eV). Upon illuminationwith electromagnetic radiation equal or higher than the bandgap, thevalence band electron is excited to the conduction band leaving anelectron hole in the valence band. The formed exciton (electron-electronhole pair) then radiatively recombines in the form of photoluminescence,with maximum intensity centered around the LC bandgap value andexhibiting photoluminescence quantum yield of at least 1%. In contactwith external electron and electron hole sources LC could exhibitelectroluminescence. In the context of the present invention LCs do notexhibit mechano-luminescence (e.g. piezoluminescence),chemiluminescence, electrochemiluminescence nor thermoluminescence.

The term “quantum dot” (QD) is known and particularly relates tosemiconductor nanocrystals, which have a diameter typically between 3-15nm. In this range, the physical diameter of the QD is smaller than thebulk excitation Bohr radius, causing quantum confinement effect topredominate. As a result the electronic states of the QD, and thereforethe bandgap, are a function of the QD composition and physical size,i.e. the color of absorption/emission is linked with the QD size. Theoptical quality of the QDs sample is directly linked with theirhomogeneity (more monodisperse QDs will have smaller FWHM of theemission). When QD reach size bigger than the Bohr radius the quantumconfinement effect is hindered and the sample may not be luminescentanymore as nonradiative pathways for exciton recombination may becomedominant. Thus, QDs are a specific sub-group of nanocrystals, defined inparticular by its size and size distribution. Properties of the QDs aredirectly linked with these parameters, distinguishing them fromnanocrystals.

The term “solvent” is known in the field and particularly includesaliphatic hydrocarbons, aromatic hydrocarbons, ethers (includingglyclol-ethers), esters, alcohols, ketones. The above organics can besubstituted or unsubstituted by one or more substituents, for example byhalogen (such as fluoro), Hydroxy, C1-4 alkoxy (such as methoxy orethoxy) and alkyl (such as methyl, ethyl, isopropyl). The above organicsinclude linear, branched and cyclic derivatives. There can also beunsaturated bonds in the molecule. The above compounds typically have4-24 carbon atoms, preferably 5-12 carbon atoms, most preferably 6-10carbon atoms.

The terms “surfactant”, “ligand”, “dispersant” and “dispersing agent”are known in the field and have essentially the same meaning. In thecontext of the present invention, these terms denote an organicsubstance, other than a solvent, which is used in suspensions orcolloids to improve the separation of particles and to preventagglomeration or settling. Without being bound to theory, it is believedthat surfactants are physically or chemically attached on the particlesurface either before or after adding the particles to the solvent andthereby provide the desired effects. The term surfactants includespolymer materials and small molecules; surfactants typically containpolar functional end-groups and apolar end-groups. In the context of thepresent invention, solvents (e.g. toluene) are not consideredsurfactants.

The term “suspension” is known and relates to a heterogeneous fluid ofan internal phase (i.p.) that is a solid and an external phase (e.p.)that is a liquid. The external phase comprises one or moredispersants/surfactants, optionally one or more solvents and optionallyone or more pre-polymers.

The term “polymer” is known and includes organic and inorganic syntheticmaterials. The term “pre-polymer” shall include both, monomers andoligomers.

The term “solution-processing” is known in the field and denotes theapplication of a coating or thin film to a substrate by the use of asolution-based (=liquid) starting material. In the context of thepresent invention, solution processing relates to the fabrication ofcommercial products, such as electronic devices, optical devices, andarticles comprising (decorative) coatings and also to the fabrication ofintermediate goods comprising a QD composite or QD layer. Typically theapplication of the suspension(s) is/are conducted at ambient conditions.

The term “QD composite” denotes a solid inorganic/organic compositematerial comprising LCs/QD, surfactant and a matrix. The form of a QDcomposite includes films, fibers and bulk material. QD composites areused for applications where the LCs/QD's only have an optical function,as the LCs/QD's are not electronically addressed.

In QD composites, the LCs/QD's are embedded in a matrix, such as apolymer matrix or an inorganic matrix, in order to spatially separatethe LCs/QD's from each other. Depending on the use, the thickness of aQD composite film may vary over a broad range, but typically is 1-1000microns.

The term “QD layer” denotes a thin layer comprising luminescent crystals(specifically QDs) and surfactant and are free of, or essentially freeof additional components, such as matrix/binder. QD layers may findvarious applications, including quantum dot light emitting diodes (QLED)or quantum dot solar cells. In these applications, the LCs/QDs areelectronically addressed; a current flows through the QD-layer byapplying a voltage. Depending on the use, the thickness of a QD layermay vary over a broad range, but typically is 3-200 nm, preferably 5-100nm, most preferably 6-30 nm. A QD layer can be composed of a monolayerof LCs/QDs, thus having a thickness equal to the size of the LCs/QDsused and thus defining a lower limit of the thickness.

The present invention will be better understood by reference to thefigures.

FIGS. 1(a) and (b) outlines the various aspects of the presentinvention. In FIG. 1 b, x-axis shows particle size, y axis shows numberof particles.

FIG. 2 shows a TEM image of typical QD's synthesized according to thepresent invention, showing the cubic nature of the crystal structure.

FIG. 3 shows an SEM image of a typical starting solid material powderprepared by precipitation.

In a first aspect, the invention relates to a method for manufacturingluminescent crystals, specifically luminescent crystals from the classof quantum dots. More specifically, the invention relates to a methodfor manufacturing luminescent crystals of 2-50 nm size, preferably 3-15nm size, said luminescent crystals being selected from compounds offormula (I)

M¹ _(a)M² _(b)X_(c)  (I),

wherein

M¹ represents one or more alkaline metals selected from Cs, Rb, K, Na,and Li

M² represents one or more metals selected from the group consisting ofGe, Sn, Pb, Sb, and Bi,

X represents one or more anions selected from the group consisting ofchloride, bromide, iodide, cyanide, thiocyanate, isothiocyanate andsulfide, preferably one or more halogenides selected from the groupconsisting of Cl, Br, and I,

a represents 1-4

b represents 1-2

c represents 3-9;

said method comprising the steps of (a) providing a solid material asdefined below; and (b) dispersing said material in the presence of aliquid as defined below.

This aspect of the invention shall be explained in further detail below.

It is known that LCs/QDs are materials sensitive to the environment.First they tend to aggregate what induces the non-radiativerecombination paths, leading to reduced luminescence quantum yield.Accordingly, measures have to be taken to stabilize the LCs/QDs oncesynthesized. The method described herein meets with this requirement bydisclosing an improved manufacturing method to provide LCs/QDs in theform of a stable suspension (“ink”).

The method described herein may be considered a “top down” approach, asmaterial is first conventionally synthesized and then reduced in sizeand stabilized to obtain LCs/QDs. This approach is opposite to what isknown and described in Kovalenko (discussed above), which is a “bottomup” approach. The inventive method is further illustrated, but notlimited by the experiments provided below.

The method described herein provides LCs/QDs having excellentproperties. First, small FWHM values (Width of the emission peak; e.g.19 nm for emission at 507 nm) are observed. Second, high luminescencequantum yields are observed (e.g. 71% for emission at 507 nm).Accordingly, the LCs/QDs provided by the inventive method are suited fora large number of applications in electronic and optical devices.Further, the LCs/QDs provided by the inventive method are also suitedfor coating (non-electronic/non-optical) articles, such as a decorativecoating.

The inventive method is superior, when compared to known manufacturingmethods. First, it is much more robust and can be easily up-scaled.Second, it requires less starting materials and produces lessby-products. Third, no solvent exchange to low-boiling solvents (e.g.toluene) is required after the LCs/QDs synthesis because the synthesiscan directly take place in low-boiling solvents. As a result, themanufacturing costs are significantly reduced, making LCs/QDs availablefor a large number of applications.

Luminescent Crystals/Quantum Dots of formula (I): The inventive methodprovides for LCs/QDs having an average size of 2-50 nm, in particular of3-15 nm. The LCs/QDs further have a narrow size distribution, asindicated by the low FWHM values of the emission peaks.

In one embodiment, the invention relates to LCs/QDs of formula (I),where a=1, b=1, c=3.

In one embodiment, the invention relates to LCs/QDs of formula (I),where M¹=Cs.

In one embodiment, the invention relates to LCs/QDs of formula (I),where M²=Pb.

In one embodiment, the invention relates to LCs/QDs of formula (I),where X is a combination of at least two elements selected from the listof Cl, Br, I.

In one embodiment, the invention relates to LCs/QDs of formula (I),selected from Cs₁Pb₁X₃, particularly CsPbBr₃, CsPbBr₂I. This embodimentalso includes corresponding molar mixtures of CsBr and PbBr2 or mixturesof CsI and PbBr2.

In one further embodiment, the invention relates to LCs/QDs of formula(I) further including doped materials, i.e. wherein part of M¹ isreplaced by other alkaline metals, or wherein part of M² is replaced byother transition metals or rare earth elements or wherein part of X isreplaced by other halogenides.

In one further embodiment the invention relates to LCs/QDs of formula(I) , selected from M¹SnX₃, M¹ ₃Bi₂X₉, M¹GeX₃.

The compounds of formula (I) include stoichiometric andnon-stoichiometric compounds. Compounds of formula (I) arestoichiometric, in case a, b and c represent a natural number; they arenon-stoichiometric, in case a, b and c represent an integer. In onefurther embodiment the invention relates to LCs/QDs of formula (I)wherein part of X is replaced by one or more anions selected from thegroup consisting of cyanide, thiocyanate, isothiocyanate and sulfide. Asexemplary embodiments are identified

M¹ _(a)M² _(b)X¹ _(c′)X² _(c″)  (I-1),

wherein

M¹, M², a, b are as identified above;

X¹ represents halogenides as identified;

X² represents an anion selected from cyanide, thiocyanate,isothiocyanate and sulfide;

c′+c″ represents a real number from 3 to 9 and c′/c″>0.9.

As sulfide is 2−, it counts twice when calculating c″.

Exemplary embodiments of formula (I-1) include CsPbCl_(2.9)CN_(0.1),CsSnBr₂ (SCN)₁, Cs₃Bi₂Br_(8.8)(NCS)_(0.2), andCsPbBr_(0.43)I_(2.43)S_(0.07).

Solid Material: Suitable Solid material provided in step (a) has anaverage particle size of at least 15 nm and a poly-disperse sizedistribution, typically 15 nm-100 μm, more typically 50 nm-50 μm. Theparticle size of the solid material shall be determined by SEM, TEM orBET.

Further, such solid material has a chemical composition that correspondsto the chemical composition of the desired LCs/QDs. Accordingly, suchsolid material has a stoichiometric composition of a moles M¹, b molesM² and c moles X.

Such material may be provided to the inventive process by differentapproaches, e.g. (a1) (a2), (a3) as outlined below. The material may beprovided to step (b) either continuously or discontinuously by knownmethods.

Wet synthetic process (a1): Manufacturing of solid material according toformula (I) is known per se. The most common methods include wetsynthetic processes such as precipitation processes from a solvent basedor aqueous phase. The material may be provided to step (b) eithercontinuously or discontinuously by known methods.

This approach may be considered “top-down”: Solid starting materialsavailable by wet synthesis exhibit a poly-disperse particle sizedistribution with an average particle size of >15 nm (measured by BET,SEM or TEM) whereas synthesized luminescent crystals exhibit a verynarrow size distribution with an average size of 2-50 nm (see FIG. 1b ).By following the methods described herein, the average particle size andpolydispersity of the starting material is reduced in order to obtain anarrow size distribution and a particle size of 2-50 nm.

Dry synthetic process in a gas phase (a2-1): An alternative approach formanufacturing of solid material according to formula (I) includes drysynthetic process in a gas phase, particularly decomposition andpyrolysis processes e.g Flame Spray Pyrolysis Process. The solidmaterials obtained by this process are typically smaller, compared to(a1).

This approach may also be considered “top-down”: Solid startingmaterials available by dry synthesis exhibit a polydisperse particlesize distribution with an average particle size of >15 nm (measured byBET, SEM or TEM) whereas synthesized luminescent crystals exhibit a verynarrow size distribution with an average size of 2-50 nm (see FIG. 1b ).Accordingly, at least part of the starting material is reduced in size.

Dry synthetic process by milling (a2-2): A further approach formanufacturing of solid material according to formula (I) includes drymilling of precursor materials. In this embodiment, the solid materialis a mixture of two or more dry precursors having the formulae aM¹ ₁X₁and M² _(b)X_((c−a)), where the substituents are defined above. Forexample, CsPbBr3, Cs4PbBr6, are accessible by corresponding molarmixtures of the precursors CsBr and PbBr2 or CsPbBr2I being accessibleby corresponding mixtures of precursors CsI and PbBr2. The drycrystalline material according to formula (I) is then obtained in a drymilling process, e.g. using a pestle and mortar or a process includingagitated milling balls. This process can be regarded as a solid statereaction induced by milling.

In situ formation (a3): A further alternative for a solid materialaccording to formula (I) includes in situ formation, such as solid statereaction during the dispersing process. In this embodiment, the solidmaterial is a mixture of two or more dry precursors having the formulaeaM¹ ₁X₁ and M² _(b)X_((c−1)), where the substituents are defined above.For example CsPbBr3, Cs4PbBr6, are accessible by corresponding molarmixtures of the precursors CsBr and PbBr2 or CsPbBr2I being accessibleby corresponding mixtures of precursors CsI and PbBr2. The crystallinematerial according to formula (I) is then formed during the dispersingprocess (i.e. in situ) by reaction of the two precursors of the solidmaterial.

The above precursors, in turn, are available by known methods, such aswet synthetic processes, dry synthetic processes. The skilled person isin a position to select suitable precursors to obtain luminescentcrystals of formula (I). Again, this approach may also be considered“top-down”, as the precursors used are larger than the the LCs/QDsobtained.

In one embodiment the average particle size of the solid material is atleast 15 nm (determined by BET, SEM or TEM), preferably between 15 nm-100 μm, more preferably 50 nm-50 μm.

In an advantageous embodiment, the solid material consists of a singlecomposition having the same stoichiometry as the final LCs/QDs offormula (I).

Step (b): Without being bound to theory, it is believed that upondispersion of the starting material in the liquid phase a number ofeffects occur simultaneously or subsequently.

First, the solid material is evenly distributed within the liquid phase.

Second, the solid material is contacted with the surfactant. It isbelieved that the material is thereby coated and stabilized in theliquid phase.

Third, the particle size of the solid material is reduced. Without beingbound to theory it is believed that a monodisperse particle sizedistribution is obtained by two occurring mechanisms: (1) mechanicalcrushing/cleaving of particles larger than the final LCs/QD size, (2)Ostwald ripening and sintering of particles smaller than the finalLCs/QD size.

In a specific embodiment, the average particle size of the solidstarting material is at least 1.5 times (preferably at least 2 times,most preferably at least 5 times) higher than the average particle sizeof the correspondingly synthesized LCs/QDs.

Liquid: As outlined above, dispersion of step (b) is performed in aliquid phase. Suitable liquids may be selected from (i) liquidsurfactants, (ii) a combination of (liquid or solid) surfactant andsolvent, (iii) a combination of (liquid or solid) surfactant, solventand (liquid or solid) pre-polymer or polymer and (iv) a combination of(liquid or solid) surfactant and liquid pre-polymer.

In embodiment (i), the liquid phase consists of (or essentially consistsof) liquid surfactants. This embodiment is advantageous, as it is asimple system without the use of solvents.

In embodiment (ii), the liquid phase consists of (or essentiallyconsists of) a combination of (liquid or solid) surfactant andsolvent(s). This embodiment is advantageous, as it allows the use ofsolid surfactants.

In embodiment (iii), the liquid phase consists of (or essentiallyconsists of) a combination of (liquid or solid) surfactant, solvent(s)and (liquid or solid) pre-polymer or polymer. This embodiment isadvantageous, as This embodiment is advantageous, as it provides acomposition that may be directly used for manufacturing intermediates asdefined below.

In embodiment (iv), the liquid phase consists of (or essentiallyconsists of) liquid pre-polymer. This embodiment is advantageous, as itprovides a composition that is free of solvents and that may be directlyused for manufacturing intermediates as defined below.

Solvent: The term solvent is defined above. For avoidance of doubt, theterm solvent does neither include surfactants nor pre-polymers.

Advantageously, the solvent is selected from the group of hydrocarbons(including linear, branched and cyclic hydro-carbons), aromatichydrocarbons, ethers (including glycol-ethers), esters, alcohols,ketones. Preferably the solvent is selected from the group of linear andbranched C₅₋₂₄ alkanes, said alkanes being unsubstituted or substitutedby phenyl or naphtyl. Most preferably, the solvent is selected from thegroup of linear C₅₋₁₅ alkanes and toluene.

In a further embodiment the solvent exhibits a boiling point below 140°C., preferably below 120° C. As a beneficial aspect of the inventivemethod, it is now possible to obtain LCs/QDs at much lower temperaturewhen compared to previous methods, such as Protesescu or Zhang (bothdiscussed above, using synthesis methods of 140-200° C.)

Pre-Polymer: The term pre-polymer is defined above. Advantageously, thepre-polymer is selected from the group of acrylates, carbonates,sulfones, epoxies, vinyls, urethanes, imides, esters, furanes,melamines, styrenes, and silicones. Preferably, the pre-polymer isselected from the group of acrylates, urethanes, styrenes. Particularlypreferably, the pre-polymer is selected from the group of acrylates.

Surfactant: A broad variety of surfactants may be used in the context ofthe present invention. Suitable surfactants may be determined in routineexperiments; its choice depends mainly on the polymer used in the nextstep and the nature of solid material. Surfactants may be selected fromthe class of non-ionic surfactants, cationic surfactants, zwitterionicsurfactants and anionic surfactants. It is known in the art to combinetwo or more surfactants to improve positive properties; such combinationof surfactants being also subject to the present invention.

Non-ionic surfactants include: maleic polymers such as Poly(maleicanhydride-alt-1-octadecene), polyamines, alkylamines, (e.g.N-alkyl-1,3-propylene-diamines, N-alkyldipropylene-triamines,N-alkyltripropylene-tetraamines, N-alkylpolypropylene-polyamines,)poly-(ethyleneimine), polyesters, alkyl esters (e.g. cetyl palmitate),alkyl polyglycol ethers (such as fatty alcohol polyglycol ether with3-25 ethoxy units (EO), e.g. Dehypon E124) and oxoalcoholpolyglycolether), mixed alkyl/aryl polyglycolethers, alkylpolyglucosides (APGs), fatty alcohols, such as stearyl alcohols (e.g.Lorol C18™)

Non-ionic surfactants further include polymeric ethoxylate and/orpropoxylate (EO/PO) adduct surfactants, such as fatty alcoholalkoxylates, alcohol EO/PO adducts (including fatty alcohol EO/POadducts, oxo alcohol EO/PO adducts), EO/PO block-copolymers, ethylenediamine ethylene oxide-propylene oxide (EO/PO) block-copolymers,endcapped (fatty) alcohol EO adducts and EO/PO adducts(e.g. butylendcapped), esters of carboxylic acids, in particular EO/PO adducts andsorbitan esters (e.g. from the group of SPAN).

Non-ionic surfactants further include alkoxy-silanes and hydrolyzedproducts thereof.

Non-ionic surfactants further include alkylphosphines, alkylphosphineoxides (e.g. trioctylphosphine oxide—TOPO) and alkylthiols.

Non-ionic surfactants further include alkyl esters of fatty acids (e.g.cetyl palmitate, lauric acid, capric acid).

A preferred class of non-ionic surfactants are alkylimines alkylamines,e.g. dioctylamine, oleylamine, octadecylamine, hexadecylamine.

Cationic surfactants include: alkylammonium halides, more specificallyalkyltrimethylammonium halides e.g. cetyltrimethylammonium bromide,dialkyldimethylammonium halides such as e.g. distearyldimethylammoniumchloride, trialkylmethylammonium halides e.g. trioctylmethylammoniumchloride, diquarternary polydimethylsiloxanes.

Zwitterionic surfactants include: betaines, such as caprylic glycinate,cocamidopropylbetain, and disodium cocoampho diacetate.

Anionic surfactants include sulfates, sulfonates, phosphates, andcarboxylates. Specific examples include phosphate esters of alkylethers, ammonium lauryl sulfate, alkali lauryl sulfate and the relatedalkyl-ether sulfates e.g. alkali laureth sulfate.

A preferred class of anionic surfactants are carboxylates from the classof fatty acids, such as oleic acid, stearic acid, palmitic acid.

In a preferred embodiment the surfactant is selected from the followinglist: SP 13300, SP 20000, SP 24000SC, SP 41000, SP540, BYK9077, HypermerKD1-SO-(AP), Span65, Span80, Span85, methoxy-ethoxy-ethoxy-acetic acid,oleylamine, oleic acid, stearic acid, Poly(maleicanhydride-alt-1-octadecene), and TOPO.

In a further preferred embodiment the surfactant is selected from thefollowing list: SP 13300, SP 20000, SP 24000SC, SP 41000, SP540,BYK9077, Hypermer KD1-SO-(AP), Span65, Span80, Span85,methoxy-ethoxy-ethoxy-acetic acid, stearic acid, Poly(maleicanhydride-alt-1-octadecene), and TOPO, hexadecylamine, octadecylamine,dioctylamine.

In a further embodiment, the surfactants are selected from the group ofanionic, cationic, non-ionic and zwitter-ionic surfactants comprisingapolar end-groups selected from the group of alkyl or alkyl-ether chainswith 4-30, preferably 6-24, most preferably 8-20 carbon atoms.

In a further embodiment, the surfactants are selected from the group ofanionic, cationic, non-ionic and zwitter-ionic surfactants having one ormore chemical moieties selected from the group of alkyl ethers with theformula RO—(C₂H₄O)_(m)(C₃H₆O)_(n)— (whereby m and n independently are0-10, but m+n>2 and whereby R is C₁₋₅-alkyl)

In a further embodiment, anionic surfactants are selected frommonocarboxylic acids comprising a polyether tail according to formula(II),

R(OC_(n)H_(2n))_(q)OCH₂C(O)OH  (II)

wherein R is C₁₋₅-alkyl, q is an integer from 0 to 5 and n is an integerfrom 1 to 3. Five particularly preferred compounds of that class are:

wherein q is from 0-4. This corresponds to a compound of formula (II),wherein R=Methyl, n=2 and q is an integer from 0-4. A particularlypreferred compound of that class is

Dispersing process: Suitable dispersing processes include dispersingmethods comprising milling balls. In a preferred embodiment thedispersing method is ball-milling preferably by the use of an agitatorball mill. In a preferred embodiment the ball size is below 5 mm,preferably below 500 microns. In a further embodiment the dispersingmethod is ball-milling with a ball size between 10-1000 μm, preferably20-500 μm. In a further embodiment the dispersing method is ball-millingwith a specific power input per weight of suspension of at least 10W/kg, preferably 100 W/kg, most preferably 1000 W/kg. In one furtherembodiment, the suspension temperature during the dispersing process isbelow 140° C., preferably below 120° C., most preferably below 70° C. Itwas surprisingly found that solid materials as defined above can beconverted to LCs/QDs with excellent optical properties (high quantumyield, small FWHM) by the use of agitated milling balls, providingLCs/QDs with excellent properties and at low reaction temperatures. Thisis considered a significant advantage over the known methods.

In a further embodiment of the inventive method, the weight ratio solidmaterial:liquid material (solvent+pre-polymer+surfactant) is in therange of 0.0001-0.5, preferably 0.0005-0.1, most preferably 0.001-0.05.

In a further embodiment of the inventive method, the weight ratiosurfactant:solid material is in the range of 100-0.1, preferably 50-0.5,most preferably 20-1.

Post-Processing: In a further embodiment, the as-synthesized LCs/QDs maybe subject to post-processing, such as outlined below in steps (b-2)(b-3), (b-4), and (b-5).

In one embodiment of such post-processing, the halide atom X ofsynthesized LCs/QD's can be replaced fully or partially with otherhalide atoms by anion exchange. In particular alkali halides, such asNaI, KI, LiI, and lead halides, such as PbI2, may be used for the anionexchange (b-2). This allows fine-tuning of the emission peak.

In a further embodiment of such post-processing two or more types ofluminescent crystals of formula (I) are mixed. By mixing different typesof luminescent crystals, e.g. by combining two suspensions comprisingsuch luminescent crystals, the emission peak of the composition istuned. (b-5)

In a further embodiment, compositions of the present inventions may bepurified from excess surfactant by diafiltration of synthesizedcompositions. (b-3)

In a further embodiment, the LCs/QD solid content of compositions of thepresent inventions may be increased by diafiltration or solventevaporation of synthesized compositions. (b-4)

In a second aspect, the invention relates to a composition in the formof a suspension, also termed “ink”, and its uses. This aspect of theinvention shall be explained in further detail below.

Accordingly, the invention also provides for a composition in the formof a suspension comprising (i) luminescent crystals of formula (I) asdescribed herein; (ii) surfactant as described herein but excludingoleyl amine, oleic acid and trioctylphosphine; and (iii) optionallysolvent as described herein; and (iv) optionally polymer or pre-polymeras described herein. Such compositions are novel and may be obtained bythe inventive method, as described in the first aspect of thisinvention.

In one embodiment the invention provides for suspensions where thequantum yield thereof is >20%, preferably >50%, most preferably >70%.

In a further embodiment the invention provides for suspensions where theFWHM of LCs/QDs for visible emissions is <50 nm, preferably, <40 nm,most preferably <30 nm.

In a further embodiment the invention provides for suspensions where theFWHM of LCs/QDs having an emission peak between 480-550 nm or between600-680 nm is <40 nm, preferably, <30 nm, most preferably <20 nm.

In a further embodiment the invention provides for suspensions where theFWHM of LCs/QDs having an emission peak between 480-530 nm is <40 nm,preferably, <30 nm, most preferably <20 nm.

The amount of components (i), (ii), (iii) and (iv) may vary over a broadrange and depends inter alia on its intended use and the nature ofsurfactant.

In one embodiment, the weight ratio luminescent crystals (i) liquidmaterial (ii)+(iii)+(iv) is in the range of 0.0001-0.5, preferably0.0005-0.3, most preferably 0.001-0.1.

In one further embodiment, the weight ratio surfactant (ii): luminescentcrystals (i) is in the range of 100-0.05, preferably 50-0.2, mostpreferably 20-1.

In one further embodiment the polymer or pre-polymer concentration is inthe range of 0.1-30 wt %, preferably 0.5-20 wt %, most preferably 1-10wt % of the total composition.

As outlined above, component (i) and (ii) are mandatory, while component(iii) and (iv) are optional. The invention thus relates to inkscontaining (i.e. comprising or consisting of):

-   -   components (i), (ii) whereby (ii) is liquid, no (iii) no (iv);    -   components (i), (ii), (iii), no (iv);    -   components (i), (ii), (iv), no (iii);    -   components (i), (ii), (iii) and (iv).

In one further embodiment, the composition comprises component (i),(ii), (iii) and (iv), wherein component (ii) comprises aromatichydrocarbons, preferably toluene and component (iv) comprises cyclicolefin copolymers.

In one further embodiment, the composition comprises component (i),(ii), (iii) and (iv), wherein component (ii) comprises linear alkanesand/or aromatic hydrocarbons and component (iv) comprises styrenecopolymers and/or styrene block-copolymers.

Solvent-free ink: The invention provides for compositions in the form ofa suspension as described herein, comprising components (i), (ii) and(iv), but which is free of, or essentially free of, solvents (iii). Inthis embodiment, the weight ratio LCs/QDs (i):liquid material(pre-polymer (iv)+surfactant(ii)) preferably is in the range of0.0001-0.5, preferably 0.0005-0.3, most preferably 0.001-0.1. Suchcomposition may be termed solvent-free inks and are particularlysuitable for supplying it to manufacturers of intermediates or devicesas discussed below.

Pre-polymers particularly suitable for solvent-free inks includeacrylates, epoxies, urethanes, silicones, styrenes. Again, the termpre-polymers includes monomers and oligomers thereof. Preferablysolvent-free inks include acrylates.

An ink is considered solvent-free when containing less than 10 wt %solvent, preferably less than 1 wt % solvent.

In a further embodiment the solvent-free ink further comprises apolymerization initiator, such as a radical photoinitiator or atemperature sensitive radical initiator.

Concentrate: The invention provides for compositions in the form of asuspension as described herein, which is free of, or essentially freeof, solvents (iii), which is free of or essentially free of pre-polymer(iv) and wherein surfactant (ii) is a liquid surfactant. In thisembodiment, the weight ratio surfactant (ii): LCs/QDs (i) preferably isin the range of 100-1, preferably 50-2, most preferably 20-10.

The inks as described herein find many applications, they areparticularly useful for converting blue light into white light,particularly with the use of a light emitting diode (LED).

In a third aspect, the invention relates to a solid polymer compositionand its uses. The term solid polymer composition denotes an organic orinorganic polymer matrix comprising LCs/QD's as described herein. Thisaspect of the invention shall be explained in further detail below.

In one embodiment (step (c)), the invention provides for a solid polymercompositions comprising (i) LCs/QDs as described herein, (ii)surfactants as described herein but excluding oleyl amine, oleic acidand trioctylphosphine and (iii) a hardened/cured polymer, preferablyselected from organic polymers.

In a further embodiment the organic polymer is preferably selected fromthe list of acrylate polymers, carbonate polymers, sulfone polymers,epoxy polymers, vinyl polymers, urethane polymers, imide polymers, esterpolymers, furane polymers, melamine polymers, styrene polymers andsilicone polymers. Accordingly, said polymer preferably containsrepeating units of pre-polymers as described herein. Furthermore thepolymer can be linear or cross-linked.

In a further embodiment the organic polymer is preferably selected fromthe list of acrylate polymers, epoxy polymers, urethane polymers,styrene polymers, silicone polymers and cyclic olefin copolymers.Accordingly, said polymer preferably contains repeating units ofpre-polymers as described herein. Furthermore the polymer can be linearor cross-linked.

In one embodiment, the organic polymer comprises styrene copolymersand/or styrene block-copolymers, preferably block-copolymers of styreneand isoprene and block-copolymers of styrene, ethylene and butene.

In one embodiment, the weight ratio LCs/QDs:matrix (polymer+surfactant)in said solid polymer composition is in the range of 0.0001-0.1,preferably 0.0005-0.05, most preferably 0.001-0.02.

In one embodiment, the weight ratio surfactant:LCs/QDs in said solidpolymer composition is in the range of 100-0.05, preferably 50-0.2, mostpreferably 20-1.

In a further embodiment the quantum yield of solid polymer compositionsof the present invention is >20%, preferably >50%, most preferably >70%

In a further embodiment the FWHM of solid polymer compositions of thepresent invention for visible emissions is <50 nm, preferably, <40 nm,most preferably <30 nm.

In a fourth aspect, the invention relates to an intermediate goodcomprising a sheet-like substrate coated with one or more layers,wherein at least one of said layers is a functional layer, wherein saidfunctional layer comprises a solid polymer composition as describedherein. This aspect of the invention shall be explained in furtherdetail below.

In an advantageous embodiment, functional layer converts blue light intowhite light. The invention thus provides for the use of a solid polymercomposition for converting blue light into white light, particularlywith the use of a light emitting diode (LED) or in a liquid crystaldisplay.

In a fifth aspect, the invention relates to novel devices/articles. Thisaspect of the invention shall be explained in further detail below.

In one embodiment (step (h)), the invention provides for a device,selected from the group of electronic devices and optical devices,wherein said device comprises a substrate and a functional layer; andwherein said functional layer comprises LCs/QDs of formula (I) asdescribed herein and surfactant as described herein, but excluding oleylamine, oleic acid and trioctylphosphine. Such device may be selectedfrom the group consisting of displays, mobile devices, light emittingdevices, and solar cells, particularly wherein the device is a liquidcrystal display or a quantum dot LED (QLED).

In one embodiment, the invention provides for an article comprising asubstrate and a coating, particularly a decorative coating, said coatingcomprises LCs/QDs of formula (I) as described herein and surfactant asdescribed herein, but excluding oleyl amine, oleic acid andtrioctylphosphine.

In a sixth aspect, the invention relates to a method of manufacturingpolymer compositions (step (d)) as described herein. The methodcomprises the steps known in the art, but by using an ink as describedherein as one, or the sole, starting material.

In a seventh aspect, the invention relates to a method of manufacturingintermediate goods as described herein. This aspect of the inventionshall be explained in further detail below.

The intermediate goods according to the present invention may beobtained by solution processes. This is considered a significantadvantage, as it enables manufacturing of all layers by simpletechnologies applicable to large areas and continuous processing.Accordingly, the invention also provides methods for manufacturing anintermediate good as described herein, said method comprising the stepof (e) providing a substrate and (f) depositing a solid polymercomposition as described herein on said substrate, preferably by coatingor printing of an ink as described herein followed by drying and/orcuring.

In an eight aspect, the invention relates to a method of manufacturingelectronic devices (step (g)) as described herein. This aspect of theinvention shall be explained in further detail below.

The manufacturing of devices starting from the above describedintermediate goods is known per se, but not yet applied to the specificintermediate goods of the present invention.

To further illustrate the invention, the following examples areprovided. These examples are provided with no intent to limit the scopeof the invention. If not stated otherwise, all of the chemicals werepurchased from Aldrich.

EXAMPLE 1 Synthesis from Solid Material Obtained by Precipitation Method

Cesium lead tribromide (CsPbBr₃) was synthesized by mixing PbBr₂ andCsBr in acidic conditions. Namely, 2 mmol PbBr₂ (0.731 g, 98% ABCR) wasdissolved in 3 ml of concentrated HBr (48%, AlfaAesar). 2 mmol CsBr(0.426 g, 99.9% ABCR) was dissolved in 1 ml H₂O and added to PbBr₂solution. A bright orange solid immediately precipitated from thesolution. The solid was filtered, washed four times with absolute EtOHand dried under vacuum for 5 h to obtain 1.12 g of pure orthorhombicCsPbBr₃ (96.8% yield). This material does not show any luminescence. SEManalysis showed that the average particle size is in the range of 0.5-6microns.

The dried CsPbBr₃ powder was added to Oleylamine (70%, Aldrich)(CsPbBr₃:Oleylamine=1:10) and Toluene (>99.7%, Fluka). The finalconcentration of CsPbBr₃ was 1%. The mixture was then dispersed by ballmilling by using Yttrium stabilized zirconia beads with a size of 200microns at ambient conditions for a period of 1 h yielding an ink withgreen luminescence. Absorption and luminescence properties of the inkwere recorded in air-equilibrated solutions placed in a 10 mm quartzcuvette with a Perkin Elmer Lambda 45 spectrophotometer and a PerkinElmer LS50B spectrofluorimeter equipped with a Hamamatsu R928 phototube,respectively. The ink was diluted with toluene until the absorbancevalue did not exceed 0.1 at the excitation wavelength.

The photoluminescence quantum yield of above ink was 71% with anemission peak centered at 507 nm. The FWHM of the emission wasdetermined as 19 nm. Fluorescein (Analytical Reference grade, Aldrich)solution in 0.1 M NaOH was used as the photoluminescence quantum yieldstandard.

TEM analysis of the ink (FIG. 2) showed the presence of cubic shapedparticles with a very narrow particle size distribution.

For the XRD analysis of the ink, QDs were precipitated by acetonitrileand dried for analysis. Cubic CsPbBr₃ was the dominant phase.

The experiment above was repeated but with pure methyl-methacrylateinstead of toluene. The final ink showed a slightly blue-shiftedemission.

EXAMPLE 2 Synthesis from Solid Material Obtained by Flame SprayPyrolysis

For the preparation of CsPbBr₃ precursor 2.5 mmol cesium acetate (0.48g, ABCR), 2.5 mmol lead 2-ethylhexanoate (1.23 g, Strem) was added to2-ethylhexanoic acid (Aldrich) and dissolved by heating the mixture for1 hour at 150° C. After cooling to room temperature 7.5 mmolbromobenzene (1.18 g, Aldrich) was added to the mixture. The obtainedsolution was diluted with xylene 1:2 by weight. The precursor was fed (9ml min⁻¹, HNP Mikrosysteme, micro annular gear pump mzr-2900) to a spraynozzle, dispersed by oxygen (9 l min⁻¹, PanGas tech.) and ignited by apremixed methane-oxygen flame (CH₄: 1.2 l min⁻¹, O₂: 2.2 l min⁻¹). Theoff-gas was filtered through a glass fiber filter (Schleicher & Schuell)by a vacuum pump (Busch, Seco SV1040CV) at about 20 m³ h⁻¹. The obtainedoxide powder was collected from the glass fiber filter. XRD analysis ofthe obtained powder confirmed the composition of CsPbBr₃. SEM analysisshowed that the average particle size is below 500 nm.

The CsPbBr₃ powder was added to Span65 (Aldrich) (CsPbBr₃:Span65=1:10)and Toluene (>99.7%, Fluka). The final concentration of CsPbBr₃ was0.2%. The mixture was then dispersed by ball milling by using Yttriumstabilized zirconia beads with a size of 50 microns at ambientconditions for a period of 30 min yielding an ink with greenluminescence. Absorption and luminescence properties of the ink wererecorded as presented in Example 1. The photoluminescence quantum yieldof above ink was 37% with an emission peak centered at 511 nm. The FWHMof the emission was determined as 25 nm.

For the XRD analysis of the ink, QDs were precipitated by acetonitrileand dried for analysis. Cubic CsPbBr₃ was the dominant phase.

EXAMPLE 3 Synthesis from Solid Material Composed of a Mixture of TwoDifferent Precursors

Commercial CsBr (99.9%, ABCR) and PbBr₂ (98%, ABCR) powders were mixedin equal molar ratio leading to a net stoichiometric composition ofCsPbBr₃. The salt mixture was added to Oleylamine (70%, Aldrich)(CsPbBr₃:Oleylamine=1:10) and Toluene (>99.7%, Fluka). The finalconcentration of CsPbBr₃ was 0.2%. The mixture was then dispersed byball milling by using Yttrium stabilized zirconia beads with a size of50 microns at ambient conditions for a period of 150 min yielding an inkwith green luminescence. Absorption and luminescence properties of theink were recorded as presented in Example 1. The photoluminescencequantum yield of above ink was 48% with an emission peak centered at 503nm. The FWHM of the emission was determined as 37 nm.

For the XRD analysis of the ink, QDs were precipitated by acetonitrileand dried for analysis. Cubic CsPbBr₃ was the dominant phase.

EXAMPLE 4 Synthesis from Solid Material Obtained by Precipitation Methodwith Different Dispersing Method

Cesium lead dibromide iodide (CsPbBr2I) was synthesized by mixing PbBr₂and CsI from methyl sulfoxide (DMSO) solutions. Namely, 1 mmol PbBr₂(0.367 g, 98% ABCR) was dissolved in 2 ml of DMSO (>99.7%, Acros). 1mmol CsI (0.259 g, 99.9%, Alfa Aesar) was dissolved in 1 ml DMSO andadded to PbBr₂ solution. After addition of 20 ml toluene (99.7%, Fluka)a bright red solid immediately precipitated from the solution. The solidwas filtered, washed four times with absolute EtOH and dried undervacuum for 5 h to obtain 0.58 g of pure orthorombic CsPbBr₂I (92.6%yield). This material does not show any luminescence.

0.02 g of the obtained salt was placed in a 30 ml glass vial containing9.78 g tetradecane (99%, Aldrich), 0.2 g oleylamine (70%, Aldrich), 10 gYttrium stabilized zirconia beads with a size of 50 microns and 3 cmmagnet bar. The mixture was mixed at 1000 rpm, 120° C. for 4 h. Aftercooling down to room temperature the ink was filtered through a 0.45 umPTFE filter and yellow luminescence was observed. Absorption andluminescence properties of the ink were recorded as presented inExample 1. The photoluminescence was characterized by an emission peakcentered at 552 nm, with FWHM of the emission peak of 30 nm.

The following further experiments were all conducted by ball millingusing similar process parameters (LCs/QDs:surfactant ratio=1:10, millingbead size=50 microns, milling time=30 min, LCs/QDs concentration in theink=0.2%, filtered by 0.45 um PTFE syringe filter for opticalcharacterization, optical characterization was identical as in Example1):

Example Solid Peak emission/ # material Surfactant solvent FWHM/QY 5CsPbBr₃ Span65 toluene Green, 506 nm/ (a1) 24 nm/42% 6 CsPbBr₃Oleylamine toluene Green, NA/NA/NA (a2) 7 CsPbBr₃ Poly(maleic tolueneGreen, NA/NA/NA (a2) anhydride-alt-1- octadecene) 8 CsPbBr₃ TOPO tolueneGreen, NA/NA/NA (a2) 9 CsPbBr₃ Span65 Butyl Green, NA/NA/NA (a2) acetate

EXAMPLE 10 Synthesis from Solid Material Obtained Via Dry Milling Method

Cesium lead tribromide (CsPbBr₃) was synthesized by milling PbBr₂ andCsBr. Namely, 2 mmol PbBr₂ (0.731 g, 98% ABCR) and 2 mmol CsBr (0.426 g,99.9% ABCR) were milled with Yttrium stabilized zirconia beads (2 mmdiameter) for 2 h to obtain 1.08 g of pure orthorhombic CsPbBr₃ (93.3%yield). This material did not show any luminescence. SEM analysis showedthat the average particle size is in the range of 0.5-6 microns.

The orange CsPbBr₃ powder was added to Oleylamine (70%, Aldrich)(CsPbBr₃:Oleylamine=5:1) and Toluene (>99.7%, Fluka). The finalconcentration of CsPbBr₃ was 1%. The mixture was then dispersed by ballmilling by using Yttrium stabilized zirconia beads with a size of 50microns at ambient conditions for a period of 1 h yielding an ink withgreen luminescence. Absorption and luminescence properties of the inkwere recorded as presented in Example 1.

The photoluminescence quantum yield of above ink was 85% with anemission peak centered at 502 nm. The FWHM of the emission wasdetermined as 19 nm.

The green emitting ink was then mixed with 10% cyclic olefin copolymer(COC, TOPAS Advanced Polymers) solution in toluene, coated on a glasssubstrate and dried at 60° C. for 15 minutes. After drying the resultingoptical properties of film were measured with a spectrofluorimeterequipped with an integrating sphere (Quantaurus Absolute PL quantumyield measuring system C1134711, Hamamatsu). The photoluminescencequantum yield of the film was 80% with an emission peak centered at 502nm. The FWHM was determined as 19 nm.

EXAMPLE 11 Post-Synthetic Adjustment of the Emission Wavelength

The solid CsPbBr₃ material from example 10 was added to Oleylamine (70%,Aldrich) (CsPbBr3:Oleylamine=2:1) and n-Heptane (99%, Aldrich). Thefinal concentration of CsPbBr₃ was 1%. The mixture was then dispersed byball milling by using Yttrium stabilized zirconia beads with a size of50 microns at ambient conditions for a period of 1 h yielding an inkwith green luminescence. Absorption and luminescence properties of theink were recorded as presented in Example 1. The photoluminescencequantum yield of above ink was 89% with an emission peak centered at 501nm. The FWHM of the emission was determined as 20 nm.

Cesium lead triiodide (CsPbI₃) was synthesized by milling PbI2 and CsI.Namely, 2 mmol PbI2 (0.922 g, 99%, Aldrich) and 2 mmol CsI (0.519 g,99%, ABCR) were milled with Yttrium stabilized zirconia beads (2 mmdiameter) for 2 h to obtain 1.387 g of pure orthorhombic CsPbI₃ (96.2%yield). This material did not show any luminescence.

The yellow CsPbI₃ powder was added to Oleylamine (70%, Aldrich)(CsPbBr₃:Oleylamine=2:1) and n-Heptane (99%, Aldrich). The finalconcentration of CsPbI₃ was 1%. The mixture was then dispersed by ballmilling by using Yttrium stabilized zirconia beads with a size of 50microns at ambient conditions for a period of 3 h yielding an ink withred luminescence. Absorption and luminescence properties of the ink wererecorded as presented in Example 1, however cresyl violet (Aldrich)solution in MeOH was used as the photoluminescence quantum yieldstandard. The photoluminescence quantum yield of above ink was 61% withan emission peak centered at 674 nm. The FWHM of the emission wasdetermined as 48 nm.

1 ml of the green emitting CsPbBr₃ ink was then mixed with 150 μl redemitting CsPbI₃ ink. The mixture changed immediately the emissionwavelength, which was found to be centered at 529 nm with thephotoluminescence quantum yield of 58% and FWHM of 21 nm. There were notraces of photoluminescence coming from original CsPbBr₃ ink (501 nm)and CsPbBrI₃ ink (676 nm) found.

In a further test, 0.5 ml of the green emitting CsPbBr₃ ink was thenmixed with 1 ml red emitting CsPbI3 ink. The mixture changed immediatelythe emission wavelength, which was found to be centered at 640 nm withthe photoluminescence quantum yield of 86% and FWHM of 37 nm. Again,there were no traces of photoluminescence coming from original CsPbBr₃ink (501 nm) and CsPbBrI₃ ink (676 nm) found.

EXAMPLE 12 Solvent-Free System

0.5 g of the green emitting ink from example 10 was mixed with 1 gPermabond UV681 UV-curable adhesive (Permabond Engineering Adhesives).The solvent present in the green emitting ink was removed by heating themixture for 90 minutes at 80° C. The remaining material was then coatedbetween two glass slides and UV cured for 30 s (UVACUBE 100, Honle UVTechnology) resulting in a solid polymeric film. The optical propertiesof resulting film were measured as in example 10. The photoluminescencequantum yield of the film was 77% with an emission peak centered at 502nm. The FWHM was determined as 19 nm.

EXAMPLE 13 Composition and Solid Polymer Composition with StyreneBlock-copolymer

0.5 g of the green emitting ink (CsPbBr₃ ink) from example 11 was mixedwith 5 g of 10 wt % polystyrene-block-polyisoprene-block-polystyrene(Aldrich, styrene 14 wt %) in toluene. The material was then coated on aglass slide and cured at 60° C. resulting in a solid polymeric film. Theoptical properties of resulting film were measured as in example 10. Thephotoluminescence quantum yield of the film was 84% with an emissionpeak centered at 501 nm. The FWHM was determined as 20 nm.

0.5 g of the green emitting ink (CsPbBr3 ink) from example 11 was mixedwith 5 g of 10 wt %Polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene(Aldrich) in n-heptane. The material was then coated on a glass slideand cured at 60° C. resulting in a solid polymeric film. The opticalproperties of resulting film were measured as in example 10. Thephotoluminescence quantum yield of the film was 83% with an emissionpeak centered at 501 nm. The FWHM was determined as 20 nm.

1. A composition in the form of a suspension comprising: (i) luminescentcrystals of 2-50 nm size of formula I):M¹ _(a)M² _(b)X_(c)  (I), wherein: M¹ represents one or more alkalinemetals selected from Cs, Rb, K, Na, and Li, M² represents one or moremetals selected from the group consisting of Ge, Sn, Pb, Sb, and Bi, Xrepresents one or more halogenides selected from the group consisting ofCl, Br, and I, a represents 1-4, b represents 1-2, c represents 3-9; and(ii) surfactant selected from the group of non-ionic, anionic, cationicand zwitterionic surfactants; and (iii) optionally solvent, said solventselected from the group of aliphatic hydrocarbons, esters, alcohols, andketones; and (iv) at least one acrylate polymer or at least one acrylatepre-polymer.
 2. The composition according to claim 1, wherein the weightratio luminescent crystals (i): liquid material (ii)+(iii)+(iv) is inthe range of 0.0001-0.5; and/or the weight ratio surfactant (ii):luminescent crystals (i) is in the range of 100-0.05; and/or wherein thepolymer or pre-polymer concentration is in the range of 0.1-30 wt %, ofthe total composition.
 3. A composition according to claim 1, whereinsaid surfactants comprise apolar end-groups selected from the group ofalkyl or alkyl-ether chains with 4-30 carbon atoms.
 4. A compositionaccording to claim 1, which is free of solvents (iii), and wherein theweight ratio luminescent crystals (i):liquid material (pre-polymer(iv)+surfactant (ii)) is in the range of 0.0001-0.5.
 5. A compositionaccording to claim 1, wherein the at least one polymer or pre-polymer(iv) comprises at least one acrylate pre-polymer, and optionally atleast one acrylate polymer.
 6. A composition according to claim 1,wherein the at least one polymer or pre-polymer (iv) comprises at leastone acrylate pre-polymer and at least one acrylate polymer.
 7. A solidpolymer composition comprising: (ii) luminescent crystals of 2-50 nmsize of formula (I):M¹ _(a)M² _(b)X_(c)  (I), wherein: M¹ represents one or more alkalinemetals selected from Cs, Rb, K, Na, and Li, M² represents one or moremetals selected from the group consisting of Ge, Sn, Pb, Sb, and Bi, Xrepresents one or more halogenides selected from the group consisting ofCl, Br, and I, a represents 1-4, b represents 1-2, c represents 3-9; and(iii) surfactant selected from the group of non-ionic, anionic, cationicand zwitterionic surfactants; and (iv) a hardened/ cured polymer,wherein the polymer comprises at least one acrylate.
 8. The solidpolymer composition according to claim 7, wherein the weight ratio ofsaid luminescent crystals matrix (polymer+surfactant) is in the range of0.0001-0.1; or the weight ratio of said surfactant:luminescent crystalsis in the range of 100-0.05.
 9. The solid polymer composition of claim7, wherein the surfactant comprises a zwitterionic surfactant.
 10. Acomposition according to claim 7 for converting blue light into whitelight.
 11. A composition according to claim 7 for converting blue lightinto white light in a light emitting diode (LED) or in a liquid crystaldisplay.
 12. An intermediate good comprising a sheet-like substratecoated with one or more layers, wherein at least one of said layers is afunctional layer, wherein said functional layer comprises a compositionaccording to claim
 7. 13. An intermediate good according to claim 12,wherein said functional layer converts blue light into white light. 14.A device, selected from the group of electronic devices and opticaldevices, wherein said device comprises a substrate and a functionallayer; and wherein said functional layer comprises luminescent crystalsof formula (I):(I):M¹ _(a)M² _(b)X_(c)  (I), wherein: M¹ represents one or more alkalinemetals selected from Cs, Rb, K, Na, and Li, M² represents one or moremetals selected from the group consisting of Ge, Sn, Pb, Sb, and Bi, Xrepresents one or more halogenides selected from the group consisting ofCl, Br, and I, a represents 1-4, b represents 1-2, c represents 3-9;surfactant selected from the group of non-ionic, anionic, cationic andzwitterionic surfactants; and at least one polymer, said at least onepolymer comprising an acrylate.
 15. The device according to claim 14,selected from the group consisting of displays, mobile devices, lightemitting devices, and solar cells.
 16. A device according to claim 14,selected from the group consisting of LCD displays or a quantum dotLEDs.
 17. An article comprising a substrate and a coating, said coatingcomprising luminescent crystals of formulaM¹ _(a)M² _(b)X_(c)  (I), wherein: M¹ represents one or more alkalinemetals selected from Cs, Rb, K, Na, and Li, M² represents one or moremetals selected from the group consisting of Ge, Sn, Pb, Sb, and Bi, Xrepresents one or more halogenides selected from the group consisting ofCl, Br, and I, a represents 1-4, b represents 1-2, c represents 3-9;surfactant selected from the group of non-ionic, anionic, cationic andzwitterionic surfactants; and at least one polymer, said at least onepolymer comprising an acrylate.
 18. A method for manufacturing anintermediate good comprising a sheet-like substrate coated with one ormore layers, wherein at least one of the layers is a functional layer,the method comprising the steps of: (a) providing a substrate, and (b)forming a solid polymer according to claim 7 to said substrate byapplying a suspension comprising the luminescent crystals, thesurfactant and at least one acrylate polymer or at least one acrylatepre-polymer, followed by drying and/or curing, said solid polymercomposition being said functional layer.